Benzothiophene-2-carboxamide s,s-dioxides for use in anti-fouling applications

ABSTRACT

A method and composition for protection against fouling of objects which come into contact with sea water or brackish water comprising a benzothiophene-2-carbomide S,S-dioxide as the essential component are described.

This application is a 371 of PCT/EP96/03941, which was filed on Sep. 9,1996.

The present invention relates to a method and composition for protectingobjects from fouling, in particular ships' hulls, screens, nets,structures, wharfs and signalling installations, which come into contactwith sea-water or brackish water.

Fouling by species of the group Lepadomorpha (goose barnacles), such asvarious Lepas and Scalpellum species, or by species of the groupBalanomorpha (acorn bamacles), such as Balanus or Pollicipes species,increases the frictional resistance of ships and as a result, due toincreased consumption of energy and frequent periods in dry dock, leadsto a significant increase in operating costs.

In addition to fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomossra groups, called collectively by thename Cirripedia (barnacle crabs) is of special importance in particular.

Benzothiophene-2-carboxamide S,S-dioxides (BCDs), a process for theirpreparation and their fungicidal action are known (DE-A41 15 184). Theiractivity against phytopathogenic fungi and dermatophytes is described inparticular. It is furthermore stated that BCDs are suitable forprotection of industrial materials against microbial change ordestruction.

Their use for treatment of mould-resistant emulsion paints is known fromU.S. Pat. No. 5,622,546, equivalented to EP 714420.

It has now been found, surprisingly, that BCDs not only attack thespecies of moulds which usually grow on paints, but also have anoutstanding antifouling action.

The application therefore relates to the use ofbenzothiophene-2-carboxamide S,S-dioxides for protection of objectsagainst fouling.

The compounds used as antifouling active compounds in this invention arerepresented by the formula (I)

in which

R¹ represents optionally substituted alkyl, or represents alkenyl oralkinyl, or represents in each case optionally substituted cycloalkyl orcycloalkylalkyl, or represents in each case optionally substitutedaralkyl, aralkenyl, aralkinyl or aryl,

R² represents hydrogen, or represents optionally substituted alkyl, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent an optionally substituted heterocyclic radical and

R³, R⁴, R⁵ and R⁶ independently of one another each represent hydrogen,halogen, cyano, nitro, alkyl, alkoxy, alkylthio, halogenoalkyl,halogenoalkoxy or halogenoalkylthio.

Compounds of the formula (I) which are preferably used are those inwhich

R¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, n- ori-nonyl, n- or i-decyl, n- or i-dodecyl or n- or i-octadecyl, orrepresents allyl, n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl,propargyl, n- or i-butinyl, n- or i-pentinyl, n- or i-hexinyl,chloromethyl, bromomethyl, chloroethyl, bromoethyl, chloropropyl,bromopropyl, cyanomethyl, cyanoethyl, cyanopropyl, hydroxymethyl,hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl,ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxycarbonylmethyl,methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl,ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl,propoxycarbonylethyl or propoxycarbonylpropyl; or further representscyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl,cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclpentylpropyl,cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, ineach case optionally substituted in the cycloalkyl part once to fourtimes in an identical or different manner by fluorine, chlorine,bromine, methyl, ethyl, n- or i-propyl, chloromethyl, dichloromethyl ortrifluoromethyl; or furthermore represents phenylalkyl, phenylalkenyl,phenylalkinyl, phenyl or naphthyl, in each case optionally substitutedin the aryl part once to three times in an identical or different mannerand in each case, where appropriate, having up to 6 carbon atomns in thestraight-chain or branched alkyl or alkenyl or alkinyl part, possiblesubstituents on the aryl in each case being: fluorine, chlorine,bromine, hydroxy, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-,s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- s- or t-butoxy,methylthio, ethylthio, trifluoromethyl, tifluoromethoxy,trifluoromethylthio, methylcarbonyl, ethylcarbonyl, methoxycarbonyl,ethoxycarbonyl, aminocarbonyl, N-methylaminocarbonyl,N,N-dimethylaminocarbonyl, N-ethylaminocrbonyl,N,N-diethylaminocarbonyl, N-formylamino, N-acetylamino,N-methyl-N-formylamino, N-methyl-N-acetyl-amino, N-ethyl-N-formylamino,N-ethyl-N-acetyl-amino, methoximinomethyl, methoximinoethyl,ethoximinomethyl, ethoximinoethyl or phenyl which is optionallysubstituted once to three times in an identical or different manner byfluorine, chlorine, bromine, methyl and/or ethyl,

R² represents hydroge, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, n- or i-pentyl, n- or i-hexyl, hydroxymethyl, hydroxyethyl,hydroxypropyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl,chloropropyl, bromopropyl, cyanomethyl, cyanoethyl, cyanopropyl,hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl,methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl,ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl,propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl,dimethylaminomethyl, diethylaminomethyl, dipropylaminomethyl,dimethylaminoethyl, diethylaminoethyl, dipropylaminoethyl,dimethylaminopropyl, diethylaminopropyl or dipropylaminopropyl or

R¹ and R², together with the nitrogen atom to which they are bonded,represent a heterocyclic radical of the formula

which is optionally substituted once, twice or three times by methyland/or ethyl, and

R³, R⁴, R⁵ and R⁶ independently of one another each represent hydrogen,fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-,i-, s- or t-butoxy, methylthio, ethylthio, trifluoromethyl,trifluoromethoxy or trifluoromethylthio.

Compounds of the formula (I) which are particularly preferably used arethose in which

R¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or ioctyl, n- or i-nonyl,n- or i-ecyl, n- or i-dodecyl, n- or i-octadecyl, or represents allyl,n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl, propargyl, n- ori-butinyl, n- or i-pentinyl, n- or i-hexinyl, chloromethyl, bromomethyl,chloroethyl, bromoethyl, chloropropyl, bromopropyl, cyanomethyl,cyanoethyl, cyanopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl,methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl,ethoxypropyl, or furthermore represents cyclopropyl, cyclopropylmethyl,cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl,cyclopentylethyl, cyclopentylpropyl, cyclohexyl, cyclohexylmethyl,cyclohexylethyl or cyclohexylpropyl, in each case optionally substitutedin the cycloalkyl part once to four times in an identical or differentmanner by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,chloromethyl, dichloromethyl or trifluoromethyl; or furthermorerepresents phenylalkyl, phenylalkenyl, phenylaikinyl, phenyl ornaphthyl, in each case optionally substituted in the aryl part once tothree times in an identical or different manner and in each case, whereappropriate, having up to 6 carbon atoms in the straight-chain orbranched alkyl or alkenyl or alkinyl part, possible substituents on thearyl in each case being: fluorine, chlorine, bromine, hydroxy, cyano,nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy,ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylcarbonyl,ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, or phenyl which isoptionally substituted once to three times in an identical or differentmanner by fluorine, chlorine, bromine, methyl and/or ethyl,

R² represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, n- or i-pentyl, n- or i-hexyl, hydroxymethyl, hydroxyethyl,hydroxypropyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl,chloropropyl, bromopropyl, cyanomethyl, cyanoethyl, cyanopropyl,hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl or ethoxypropyl, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent a heterocyclic radical of the formula

which is optionally substituted once, twice or three times by methyland/or ethyl, and

R³, R⁴, R⁵ and R⁶ independently of one another in each case representhydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,n-, i-, s- or t-butoxy, methylthio, ethylthio, trifluoromethyl,trifluoromethoxy or trifluoromethylthio.

Compounds of the formula (I) which are especially preferably used arethose in which

R¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, n- ori-nonyl, n- or i-decyl, n- or i-dodecyl or n- or i-octadecyl, orrepresents allyl, n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl,propargyl, n- or i-butinyl, n- or i-pentinyl, n- or i-hexinyl,chloromethyl, bromomethyl, chloroethyl, bromoethyl, chloropropyl,bromopropyl, cyanomethyl, cyanoethyl, cyanopropyl, hydroxymethyl,hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl,ethoxymethyl, ethoxyethyl or ethoxypropyl, or furthermore representscyclopropylmethyl, cyclopropylethyl, cyclopropyipropyl, cyclopentyl,cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexyl,cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, in each caseoptionally substituted in the cycloalkyl part once to four times in anidentical or different manner by fluorine, chlorine, bromine, methyl,ethyl or n- or i-propyl; or furthermore represents phenylalkyl,phenylalkenyl, phenylalkiyl, phenyl or naphthyl, in each case optionallysubstituted in the aryl part once to three times in an identical ordifferent manner and in each case, where appropriate, having up to 6carbon atoms in the straight-chain or branched alkyl or alkenyl oralkinyl part, possible substituents on the aryl in each case being:fluorine, chlorine, bromine, hydroxy, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-,i-, s- or t-butoxy, methylthio, ethylthio, trifluoromethyl,trifluoromethoxy or trifluoromethylthio, or phenyl which is optionallysubstituted once to three times in an identical or different manner byfluorine, chlorine, bromine, methyl and/or ethyl,

R² represents hydrog methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, n- or i-pentyl, n- or i-hexyl, hydroxymethyl, hydroxyethyl,hydroxypropyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl,chloropropyl, bromopropyl, cyanomethyl, cyanoethyl or cyanopropyl, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent a heterocyclic radical of the formula

which is optionally substituted once, twice or three times by methyland/or ethyl, and

R³, R⁴, R⁵ and R⁶ independently of one another in each case representhydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, methylthio, ethylthio,trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

The benzothiophene-2-carboxamide S,S-dioxides are accessible by theprocesses mentioned in EP 0 512 349.

The BCDs can be used as individual active compounds or else incombination with active compounds usually employed in the antifoulingsector. These can preferably be heavy metals, such as tin or Cu, orheavy metal compounds, such as, for example, bis(trialkyltin) sulphides,tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide,triethyltin chloride, tri-n-butyl(2-phenyl4-chlorophenoxy)-tin,tributyltin oxide, molybdenum disulphide, antimony oxide, polymericbutyl titanate, phenyl-bispyridine)-bismuth chloride, tri-n-butyltinfluoride, manganese ethylenebisdithiocarbamate, zincdimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, the zinc saltor copper salt of 2-pyridinethiol 1-oxide,bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, zinc oxide,copper(I) ethylene-bis-dithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides.

The action spectum of the N-alkylbenzothiophene-2-carboxamideS,S-dioxides is extended further or particular effects are achieved bythese combinations of active compounds. Synergistic effects are obtainedin many cases. The synergistic effect manifests itself particularlyclearly if the active compound combinations are present in certainweight ratios. However, the weight ratios of the active compounds in theactive compound combinations can vary within a relatively wide range.

Other combination partners which are suitable for the antifoulingcompositions according to the invention are, preferably, algicides,fungicides, insecticides, molluscicides and bactericides, such as, forexample:

Triazoles:

azaconazole, bromuconazole, cyproconazole, dichlobutrazole,diniconazole, hexconazole, metconazole, penconazole, propiconazole,tebuconazole, amitrole, azocyclotin, epoxyconazole, bitertanol,difenoconazole, fenbuconazole, fenchiorazole, fenethanil,fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos,myclobutanil, paclobutral,(±)-cis-1-(4-chlorophenyl)2-1H-1,2,4triazol-1-yl)-cycloheptanol,tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole,triticonazole, uniconazole and metal salts and acid adducts thereof.

Imidazoles:

imazalil, pefurazoate, prochloraz, triflumizole.

Thiazolecarboxanilides such as2′,6′-dibromo-2-methyl4-trifluoromethoxy4′-trifluoromethyl-1,3-thiazole-5-carboxanilideand metal salts and acid adducts thereof.

Succinate dehydrogenase inhibitors, such as:

fenfuram, furcarbanil, cyclafluramid, furmecyclox, Seedvax, metsulfovax,pyracarbolid, oxycarboxin, Shirlan, mebenil (mepronil), benodanil,flutolanil (Moncut);

Naphthalene derivatives, such as:

terbinafme, naftifine, butenafine;

Sulfenamides, such as dichlofluanid, tolylfluanid, folpet, fluorfolpet;captan, captofol;

Benzimidazoles, such as carbendazirm, benomyl, furahiocarb,fuberidazole, thiophanate-methyl, thiabendazole or salts thereof;

Morpholine derivatives, such as tridemorph, fenpropimorph, falimorph,dimethomorph, dodemorph; aldimorph, fenpropidin and its arylsulphonicacid salts, such as, for example, p-toluenesulphonic acid andp-dodecylphenyl-sulphonic acid;

Dithiocarbamates, such as cufraneb, ferbam, mancopper, mancozeb, maneb,metam, metiram, thiran zeneb, ziram;

Benzothiazoles, such as 2-mercaptobenzothiazole;

Benzamides, such as 2,6dichloro-N(4-trifluoromethylbenzyl)-benzamide;

Boron compounds, such as boric acid, boric acid esters, borax;

Formaldehyde and compounds which split off formaldehyde, such as benzylalcohol mono-(poly)-hemiformal, oxazolidines, hexa-hydro-S-triazines,N-methylolchloroacetamide, paraformaldehyde, nitropyrin, oxolinic acid,tecloftalam;

Tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-(cyclo-hexyldiazeniumdioxy)-tributyltin or K salts,bis-N-cyclohexyldiazeniumdioxy)-copper.

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one, N octyl-isothiazolin-3-one,4,5-trimethylene-isothiazolinones, 4,5-benzisothiazolinones;

Aldehydes, such as cinnamaldehyde, formaldehyde, glutaraldehyde,β-bromocinnamaldehyde; thiocyanates, such asthiocyanatomethylthiobenzothiazole, methylene bisthiocyanate and thelike;

quaternary ammonium compounds, such as benzyldimethyltetradecylammoniumchloride, benzyldimethyldodecylammonium chloride,didecyldimethylammonium chloride;

Iodine derivatives, such as diiodomethyl p-tolyl sulphone,3-iodo-2-propinyl alcohol, 4-chloro-phenyl 3-iodopropargylformal,3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallylalcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyln-butyl-carbamate, 3-iodo-2-propinyl-n-butyl-urea, 3-iodo-2-propinyln-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate,3-iodo-2-propinyl phenylcarbamate;

Phenol derivatives, such as tribromophenol, tetrachlorophenol,3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol,dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol,2-benzyl-4-chlorophenol and alkali metal and alkaline earth metal saltsthereof.

Microbicides having an activated halogen group, such as chloroacetamide,N-methylolchloroacetamide, bronopol, bronidox, tectamer, and such as2-bromo-2-nitro-1,3-propanediol, 2-bromio-4′-hydroxy-acetophenone,2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane,β-bromo-β-nitrostyrene;

Pyridines, such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Cu, Mn,Zn salts), tetraloro-4-methylsulphonylpyridine, pyrimethanol,mepanipyrim, dipyrithione;

Metal soaps such as tin, copper or zinc naphthenate, octoate,2-ethylhexanoate, oleate, phosphate or benzoate;

Metal salts, such as copper hydroxycarbonate, sodium dichromate,potassium dichromate, potassium chromate, copper sulphate, copperchloride, copper borate, zinc fluorosilicate, copper fluorosilicate.

Oxides, such as tributyltin oxide, Cu₂O, CuO, ZnO;

Dialkyldithiocarbamates such as Na and Zn salts ofdialkyldithiocarbamates, tetramethylthiuram disulphide, potassiumN-methyl-dithiocarbamate;

Nitriles, such as 2,4,5,6-tetrachloroisophthalodinitrile, disodiumcyanodithioimidocarbamate;

Quinolines, such as 8-hydroxyquinoline and Cu salts thereof;

mucochloric acid, 5-hydroxy-2(5H)-furanone;

4,5-dichlorodithiazolinone,4,5-benzodithiazolinone,4,5-trimethylenedithiazolinone,4,5-dichloro-(3H)-1,2-dithiol-3-one,3,5-dimethyl-tetrahydro 1 ,3,5-thiadiazine-2-thione;

N-(2-p-chlorobenzoylethyl)-hexaminium chloride, potassiumN-hydroxymethyl-N′-methyl dithiocarbamate,

2-oxo-2-(4-hydroxy-phenyl)acetohydroximic acid chloride,

phenyl 2-chloro-cyano-vinyl sulphone,

phenyl 1,2-dichloro-2-cyano-vinyl sulphone;

Ag, Zn or Cu-containing zeolites, by themselves or included in polymericactive compounds.

Mixtures having a good action are furthermore also prepared with thefollowing active compounds:

Fungicides:

Methyl (E)-methoximino[α-(o-tolyloxy)-o-tolyl]acetate, methyl(E)2-{2-[6-(2-cyanophenoxy)-pyrimidineyl-4-yl-oxy]phenyl}-3-methoxyacrylate,

acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate,chinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet,diclomezine, dichloram, diethofencarb, dimetirimol, diocab, dithianon,dodine, drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol,fenitropan, fentin acetate, fentin hydroxide, ferimzone, fluazinam,fluromide, flusulfamide, flutriafol, fosetyl, fthalide, furalaxyl,guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl,methasulfocarb, nitrothalisopropyl, nuarimol, oflurace, oxadiyl,perflurazoate, pencycuron, phosdiphen, pimaricin, piperalin,procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilon,quintozene, tar oils, tecnazene, thcyofen, thiophanate-methyl,tolclofos-methyl, triazoxide, trichlamide, tricyclazole, triforine,vinclozolin.

Insecticides:

Phosphoric acid esters, such as azinphos-ethyl, azinphos-methyl,α-1(4-chlorophenyl)-4-(O-ethyl, S-propyl)phosphoryloxy-pyrazole,chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon,dichlorvos, dimethoate, ethoate, ethoprophos, etrimfos, fenitrothion,fenthion, heptenophas, parathion, parathion-methyl, phosalone, phoxim,pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos,triazophos and trichlorphon;

Carbamates, such as aldicarb, bendiocarb, α-2-(1-methylpropyl)-phenylmethylcarbamnate, butocarboxim, butoxycarboxim, carbaryl, barbofurancarbosulfan, cloethocab, isoprocarb, methomyl, oxamyl, primicarb),promecarb), propoxur and thiodicarb;

Organosilicon compounds, preferably dimethyl(phenyl)silyl-methyl3-phenoxybenzyl ethers, such as dimethyl-(4-ethoxyphenyl)-silylmethyl3-phenoxy-benzyl ether or

(dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridylmethyl ethers, such as,for example,dimethyl-(9-ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridylmethyl etheror [(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes such as, forexample(4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl-propyl]dimethyl-silane,silafluofen;

Pyrethroids, such as allethrin, alphamethrin, bioresmethrin, byfenthrin,cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin,deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl2,2-dimethyl-3-(2-chloro-2-trifluoro-methylvinyl)cyclopropane-carboxylate,fenpropathrin, fenfluthri fenvalerte, flucythirinate, flumethrin,fluvalinate, permethrin, resmethrin and tralomethrin;

Nitroimines and nitromethylenes, such as1-[(6-chloro-3-pyridinyl)methyl]4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid),N-[(6-chloro-3-pyridyl)methyl-]N²-cyano-N¹-methylacetamide (NI-25);

Abamectin, AC 303, 630, acephate, acrinathrin alanycarb, aldoxycarb,aldrin, amitraz, azamethiphos, Bacillus thuringiensis, phosmet,phosphamidon, phosphines, prallethrin, propaphos, propetamphos,prothoate, pyraclofos, pyrethrins, pyridaben, pyridafenthion,pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodiumhexafluorosilicate, sulfotep, sulphuryl fluoride, tar oils,teflubenzuron, tefluthrin, temephos, terbufos, tetrachlorvinphos,tetramedirin, o-2-tert-butyl-pyrimidin-5-yl O-isopropylphosphorothioate, thiocyclam, thiofanox, thiometon, tralomethrin,triflumuron, trimethacarb, vamidothion, verticillium lacanii, XMC,xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin,MERbioallethrin (S)-cyclopentenyl isomer, bromophos, bromophos-ethyl,buprofezin, cadusafos, calcium polysulphide, carbophenothion, cartap,quinomethionat, chlordane, chlorfenvinphos, chlorfluazuron, chlomephos,chloropicrin, chlorpyrifos, cyanophos, beta-cyfluhrin,alpha-cypermedirin, cyophenothrin, cyromazine, dazomet, DDT,demeton-S-methylsulphon, diafenthiuron, dialifos, dicrotophos,diflubenzuron, dinoseb, deoxabenzofos, diaxacarb, disulfoton, DNOC,empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion,etofenprox, fenobucarb, fenoxycarb, fensulfothion, fipronil,flucycloxuron, flufenprox, flufenoxuron, fonofos, formetanate,formothion, fosmethilan, furathiocarb, heptachlor, hexaflumuron,hydramethylnon, hydrogen cyanide, hydroprene, IPSP, isazofos,isofenphos, isoprothiolane, isoxathion, iodfenphos, kadethrin, lindane,malathion, mercarbam, mephosfolan, mercurous chloride, metam,Metarthizium anisopliae, methacrifos, methamidophos, methidathion,methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb,mevinphos, monocrotophos, naled, Neodiprion sertifer

NPV, nicotine, omethoate, oxydefmeton-methyl, pentachorophenol,petroleum oils, phenothrin, phenthoate, phorate;

Molluscicides:

Fentin acetate, metaldehyde , methiocarb, niclosamide, thiodicarb,trimethacarb;

Algicides;

Copper sulphate, dichlorosphen, endothal, fentin acetate, quinoclamine;

Herbicides:

Diuron, dichlorophen, endothal, fentin acetate, quinochlamine.

Synergistic effects are also to be observed for these combinations.

Suitable combination partners for the BCDs are preferably algicides,such as diuron, dichlorophen, endothal, fentin acetate or quinoclamine,molluscicides, such as fentin acetate, metaldehyde, methiocarb,niclosamide, thiodicarb and trimethacarb, fungicides, such asdichlofluanid, tolylfluanid, iodopropargyl butylcarbamate, fluorfolpetand azoles, such as tebuconazole or conventional antifouling activecompounds, such as 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,tetrabutyldistannoxane,2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,4,5-dichloro-2-n-octyl-4-isothiazolin-3-one,2,4,5,6-tetrachloroisophthalodintrile, tetramethylthiuram disulphide,2,4,6-trichlorophenylmaleimide,2,3,5,6-tetra-chlor-4-(methylsulphonyl)-pyridine, diiodomethylparatrylsulphone, thiabendazole, tetra-phenylboron-pyridine salt, and the copperand sodium salt of 2-pyridinethiol 1-oxide.

The BCDs in their use in antifouling conmpositions furthermore comprisethe customary constituents, such as are described, for example, inUngerer, Chem. Ind. 37 (1985), 730-732 and Williams, Antifouling MarineCoatings 1973, Park Ridge: Noyes 1973.

In addition to the active compounds mentioned or their combinations,antifouling compositions therefore comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene rubbers,butadiene/acrylonitrile rubbers, butadiene/styrene/acrylonitrilerubbers, drying oils, such as linseed oil, asphalt and epoxidecompounds, resin esters or modified hard resins in combination with taror bitumens, small amounts of chlorinated rubber, chlorinatedpolypropylene and vinyl resins.

If appropriate, the antifouling compositions also comprise inorganicpigments, organic pigments or dyestuffs, which are preferably insolublein sea water. The antifouling compositions can furthermore comprisematerials such as colophony, in order to allow controlled release of theactive compounds or of the active compound combinations. The antifoulingcompositions can furthermore comprise plasticizers, modifying agentswhich influence the rtheological properties and other conventionalconstituents. The compounds of the formula (I) or abovementionedcombinations can also be incorporated into self-polishing antifoulingsystems.

The antifouling composition preferably comprises the BCDs inconcentrations of 1 to 20% by weight.

The compositions according to the invention advantageously allow thecompositions available to date to be replaced by more effectivecompositions. They show a good stability and advantageously have a broadaction spectrum.

EXAMPLE 1

A 2% strength solution of N-cyclohexyl-benzothiophene-2 -carboxamideS,S-dioxide is added in various dilutions to still liquid minerl saltagar.

After solidification of the agar, 1 ml of the liquid mineral salt mediumis additionally pipetted onto the agar and the plates are inoculatedwith the alga Oscillatoria tenuis. After an incubation period of 2 weeksat room temperature under irradiation with light, the growth of the algawas rated.

No alga growth was detected at concentrations from 20 ppm

What is claimed is:
 1. A method for protecting an object from fouling byat least one species selected from the group consisting of species ofthe groups Lepadomorpha, Balanomorpha and sessile Entomostraca, or by acombination of said at least one species and another organism capable offouling said object, said method comprising apply to said object anantifouling effective amount of a compound of formula (I):

in which R¹ represents optionally substituted alkyl, or representsalkenyl or alkinyl, or represents in each case optionally substitutedcycloalkyl or cycloalkylalkly, or represents in each case optionallysubstituted aralkyl, aralkenyl, aralkinyl or aryl, R² representshydrogen, or represents optionally substituted alkyl, or R¹ and R²,together with the nitrogen atom to which they are bonded, represent anoptionally substituted heterocyclic radical and R³, R⁴, R⁵ and R⁶independently of one another each represent hydrogen, halgen, cyano,nitro, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy orhalogenoalkylthio.
 2. The method according to claim 1 wherein the objectis to be protected from fouling by Cirripedia.